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Green Chemistry Synthesis Of Several Types Of Organic Carbon And Nitrogen Compounds (oxygen)

Posted on:2009-01-25Degree:MasterType:Thesis
Country:ChinaCandidate:J J WangFull Text:PDF
GTID:2191360272472710Subject:Organic Chemistry
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With the rapid development of green chemistry, green organic synthesis becames a new frontier in organic synthesis in the 21th century. In this thesis, based on the principle of Green synthesis and "Atom Economy", several functional organic molecules were synthesis and characterization. This thesis consists of four parts.The first part, green organic synthesis, as a new frontier of green chemistry, was reviewed which included the "green" starting material, "green" reaction process, "green" catalysts and "green" solvent. Finally, we illuminated the intention and significance of our research.The second part, 3,4-Dihydropyrimidin-2(1H)-ones and its derivatives were prepared using CuCl2·2H2O as the catalyst by the Biginelli reaction in microemulsion synthesis. 3,4-Dihydropyrimidin-2(1H)-ones and its derivatives have extensive application in the realm of antimicrobes, antiviral, antitumor, anti-inflammatory, antibacterial and antimould due to their important therapeutic and pharmacological properties. They are usually used for synthesis of many peroral medicines, such as calcium channel blockers,α1a-antagonists and neuropeptide antagonists, antihypertensive agents. Biginelli reaction is a significant path for synthesis of 3,4-Dihydropyrimidin-2(1H)-ones and its derivatives. Several improved procedures of Biginelli reaction have been reported, various Lewis acid catalysts, solid phase synthesis, ionic liquid and ultrasonic, microwave accelerate means, and so on. Besides, participants of Biginelli reaction also have many changes, different types of aliphatic aldehyde, aromatic aldehyde, substituted urea and thiourea and new style 1,3-dicarbonyl compounds used in Biginelli reaction have been reported recently. Microemulsion is a high-dispersed and stabilized thermodynamic system, where the micells produced by dispersed phase are in nanometer size. Such especial micro-environment can affect chemical reaction, intensifying some reactions in liquid-liquid phase. We designed a new procedure for synthesis 3,4-Dihydropyrirnidin-2(1H)-ones and its derivatives using CuCl2·2H2O as the catalyst by the Biginelli reaction in sodium dodecylsulfonate microemulsion. The advantages of this method involved the broader application scope of substrates, the more environmental friendly process and the low-cost of the Lewis acid catalyst.The third part, coumarin derivatives were prepared using CuCl2 or CuBr2 as catalysts by Pechmann reaction under solvent-free condition. Solvent-free organic reactions have attracted many interests in chemical industry. Indeed, solvent-free can make the hige reaction concentration and reaction ratio. Therefore, solvent-free reactions can proceed more efficiently and selectively than solution case. Solvent-free reaction is a more ideal mean of organic synthesis. The coumarin derivatives have attracted much attention due to their antibacterial, anticoagulants, antiallegric, hypotensive, anti-HIV and anticancer activities. Furthermore, coumarin derivatives have also been extensively used as optical bleaching agents, luminescent probes, active media for tunable dye lasers, and non-linear optical materarial since their excellent optical propertie. In this part, several coumarin derivatives using CuCl2 or CuBr2 as catalysts by Pechmann reaction under solvent-free condition were prepared. This synthetic strategy compared with raditional solution protocols has seveval advantages, such as no organic solvent pollution, elevated reaction rate, high yield and simple work-up procedure.Enaminones became an important intermediate in heterocyclic synthesis due to their multi-functional group. It has been receiving considerable attentions for long. Lots of heterocyclic compounds were prepared from Enaminones, such as pyrrole, oxazoles, pyridinones, quinolines, dibenzodiazepines, tetrahydrobenzoxazines and so on. Enaminone compounds have various reactivities and plentiful structural chemistry properties, and have important applications in the fields of biology, catalysis and materials science. For these reasons, an easy environmentally benign method for the synthesis ofβ-enaminones starting from 1,3-diketones and different amines catalysis by Mg(ClO4)2 were reported in the forth part of this thesis. The method has simple work-up procedure, mild reaction conditions and high yields virtue.
Keywords/Search Tags:Green Synthesis, Lewis acid, 3,4-Dihydropyrimidin-2(1H)-ones, Coumarin derivatives, β-Enaminones
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